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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Understanding Process–Structure Relationships during Lamination of Halide Perovskite Interfaces

Fabrication of halide perovskite (HP) solar cells typically involves the sequential deposition of multiple layers to create a device stack, which is limited by the thermal and chemical incompatibility of top contact layers with the underlying HP semiconductor. One emerging strategy to overcome these restrictions on material selection and processing conditions is lamination, where two half-stacks are independently processed and then diffusion bonded to complete the device. Lamination reduces the processing constraints on the top side of the solar cell to allow new device designs, expanded use of deposition methods, and self-encapsulation of devices. While laminated perovskite solar cells with high efficiencies and novel interlayer combinations have been demonstrated, there is a limited understanding of how the lamination process parameters affect the diffusion-bond quality and material properties of the resulting HP layer. In this study, we systematically vary temperature, pressure, and time during lamination and quantify the resulting impacts on bonded area, grain domain size, and photoluminescence. A design of experiments is performed, and statistical analysis of the experimental results is used to quantitatively evaluate the resulting process–structure–property relationships. The lamination temperature is found to be the key parameter controlling these properties. Furthermore, a temperature of 150 °C enables successful bonding over 95% of the substrate area and also results in increases in apparent grain domain size and photoluminescence intensity. Based on these insights, the lamination temperature of functional perovskite solar cell devices is varied, demonstrating the importance of the resulting bond quality on device performance metrics.

14 SOLAR ENERGY↗
DOE OSTI2025

P-Type Doping of Mixed Tin–Lead Halide Perovskites Using Electron Transfer to Mo(tfd-COCF3) 3 and F 4 TCNQ

Mixed tin-lead halide perovskites are emerging as promising candidates to address the toxicity issues of lead-based perovskites and to provide additional bandgap tunability for optoelectronic applications. Electron-transfer doping offers a prospective pathway to modulate electronic properties of metal-halide perovskites, while not disturbing the underlying crystal structure. However, limited research exists comparing molecular dopants for these systems. Here, our study investigates the p-type electron-transfer doping of the mixed tin-lead halide perovskite MAPb 0.5 Sn 0.5 I 3 (MA = methylammonium) using a sequential deposition approach (perovskite film followed by dopant incorporation) and the molecular dopants F 4 TCNQ and Mo(tfd-COCF 3 ) 3 . Up to 3 orders of magnitude higher carrier density and up to 2 orders of magnitude greater conductivity are achieved relative to the undoped samples, with F 4 TCNQ and Mo(tfd-COCF 3 ) 3 demonstrating similar doping efficiencies (associated with the ratio of mobile charges added to the number of dopant molecules incorporated) of 0.031(3) % and 0.024(3) %, respectively. Differences in the doping effectiveness for a given molarity doping solution likely follow from variations in dopant incorporation within the film during the spin coating deposition step.

14 SOLAR ENERGY↗
DOE OSTI2023

Synthesis and Characterization of Amorphous Lawsone Polymer Dots for Fluorescent Applications

In this work, a two-step hydrothermal/solvothermal process was developed to generate highly fluorescent lawsone polymer dots (LPDs) utilizing an inexpensive and abundant starting material, 2-hydroxy-1,4-napththoquinone (lawsone). This hydrothermal/solvothermal process produces LPDs that have excitation independent emission with well-defined electronic transitions. This two-step protocol provides a straightforward approach to remove unwanted small molecular fluorescence, which has plagued carbon dot systems, without the need for advanced chromatographic purification methods or steps. A series of spectroscopic, electrochemical, and theoretical experiments suggest that this process proceeds via a sequential dehydration and dehydrogenation pathway to cross-link the lawsone into a carbon dot structure. This polymerization process helps to stabilize and favor certain electronic transitions inherently present in the lawsone monomer. The generation of the LPDs results in a 2 order of magnitude increase in the emission intensity and a quantum yield of 37%. This behavior is likely the result of the cross-linked structure shielding these electronic states from deactivation caused by nonradiative processes such as vibrational coupling and excited state quenching from thermal deactivation and solvent collisions. This finding is consistent with a cross-linked enhanced emission (CEE) mechanism, as previously observed for other similar systems. The LPDs were then incorporated into a TiO2 photoanode and utilized as a photosensitizer in a dye-sensitized solar cell (DSSC) which showed an enhancement in photocurrent density over pure TiO2. We also prepared a derivative of the LPDs utilizing a diethylene triamine additive (nitrogen-doped lawsone polymer dots (N-LPDs)) using the same two-step protocol and demonstrated its potential as a fluorescence microscopy dye for imaging MDA-MB-231 cancer cells.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Multilayered Cu-Carbon Nanotube Composites for Advanced Conductors

Improving the efficiency of electrical components is critical in reducing energy consumption for various industrial and residential applications, ranging from rotating machinery to all electric devices and electric vehicle (EV) components to power grid systems. Substituting Cu wires with reduced resistance conductors that incorporate carbon nanotubes (CNTs) into Cu─ultraconductive Cu (UCC) composites─has recently been considered a promising strategy to improve energy efficiency, power density, and/or performance across various applications. Here, in this study, we created stable material formulations [CNT-containing polyvinylpyrrolidone (PVP) in dimethylformamide (DMF) solution] and utilized commercially viable fabrication approaches (electrospinning and magnetron sputtering) that produced high-performance multilayered tape-based UCC composite architectures. Increasing the CNT volume fraction by sequential layering of the structure with additional Cu-CNT layers showed a nearly stepwise improved performance in electrical and mechanical properties. This study also provides valuable insight into the effectiveness of nitrogen doping in modifying the conductivity of the CNT matrix. Fabricated prototypes demonstrated a >10% increase in current carrying capacity and >10% improvement in mechanical strength compared to those obtained on pure Cu. We believe that the properties demonstrated here, combined with the scalable manufacturing pathway of our approach, pave the way in designing future advanced conductors for diverse energy efficient and high-performance electrical systems and applications.

Carbon nanotubes↗
DOE OSTI2020

Ethanol Conversion over La 0.7 Sr 0.3 MnO 3–x (100): Autocatalysis, Adjacent O-Vacancies, Disproportionation, and Dehydrogenation

The mechanism for catalytic conversion of ethanol over La 0.7 Sr 0.3 MnO 3– x (100) surface to acetaldehyde and ethene was investigated. Pre-exposure temperature-programmed reaction (PE-TPR) experiments were performed in which ethanol was introduced to oxidized or reduced surfaces followed by heating. In particular, sequential PE-TPR experiments were conducted to incrementally and gradually reduce the surface. The products and their ratios were investigated as a function of surface reduction. The data show that acetaldehyde and ethene production is catalyzed with hydrogen abstraction and oxygen abstraction reactions occurring by intermediates in vacancies at various temperatures >400 K. Adsorption of acetaldehyde followed by a temperature-programmed reaction does not produce ethene, indicating that acetaldehyde is not an intermediate to ethene and that the hydrogen and oxygen abstraction from ethanol to ethene are decoupled steps. Further evidence for this mechanistic nuance was obtained using isotopically labeled ethanol (CD 3 CH 2 OH), which produces CD 3 CHO and CD 2 CH 2 . Additionally, the ratio of aldehyde production to alkene production increases with reduction, suggesting that aldehyde is produced from a disproportionation reaction between ethoxy species in adjacent O-vacancies, while ethene is produced from a dehydrogenation reaction with ethoxy species in vacancies without requiring adjacent O-vacancies. Counterintuitively, this finding indicates that the more oxygenated product (aldehyde vs ethene) is favored with more vacancies and that the net alcohol conversion is autocatalytic. Density functional theory calculations were able to find the previously unknown disproportionation pathway between ethoxies in adjacent O-vacancies, and kinetic Monte Carlo simulations support this interpretation by reproducing experimental selectivities. The activation energies for these pathways are estimated as 132 ± 10 kJ/mol for the disproportionation reaction (when occurring between ethoxies in adjacent vacancies) and as 148 ± 11 kJ/mol for the direct dehydrogenation reaction of an ethoxy in a vacancy. Based on these results, a mechanism with operative pathways based on elementary steps in O-vacancies is reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Computational and Experimental Mechanistic Insights into the Ethanol-to-Butanol Upgrading Reaction over MgO

The mechanism of ethanol upgrading to higher products is still under debate, especially regarding intermediate species and hydrogenation and dehydrogenation steps. In this work, we conducted a combined theoretical and experimental approach to contribute to this discussion. For such, detailed electronic structure density functional theory calculations (aiming at probing density of states, infrared spectra, geometric parameters, charge densities, and reaction energetics) and diffuse reflectance infrared Fourier transform spectroscopy experiments were carried out revealing the relevance of an appropriate combination of reactive surface sites to support the formation of several intermediates that are formed in the C-C coupling over MgO. The roles of Mg and O sites were also studied under an electronic perspective and different geometrical arrangements. We found that a kink configuration was the most adequate for ethanol to 1-butanol upgrading. Our calculations also gave us arguments to propose distinct reaction routes, whose mutual predominance would depend upon reaction temperature. At temperatures up to 573 K, the so-called β-route, which goes through scission of a Cβ-H bond and formation of an oxametallacycle-like intermediate, would dominate the coupling, whereas at higher temperatures, up to 673 K, a more usual Guerbet mechanism, via an aldol coupling step and then consecutive hydrogenations, would be expected. Here, the theoretical conclusions were followed by a careful experimental strategy using sequential experimental planning techniques in order to estimate accurate parameters with the lowest possible experimental load. Information from these different sources were coupled to develop a mathematical model for the rate of the ethanol upgrading reaction, using a Langmuir-Hinshelwood-Hougen-Watson approach. The developed and statistically validated model adequately described the experimental data at 673 K and 1.1 bar total pressure for ethanol partial pressures in the range from 0 to 20 kPa.

09 BIOMASS FUELS↗
DOE OSTI2021

Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling

Catalytic hydrodechlorination is a promising strategy for treating industrial 1,2-dichloroethane wastes, for which Pt and Pt-based alloy catalysts are widely used. Here, we performed a detailed mechanistic study for 1,2-dichloroethane hydrodechlorination on Pt using a synergistic approach combining density functional theory (DFT) calculations, reaction kinetics experiments, and microkinetic modeling. Using planewave DFT calculations, we evaluated the reaction energy and activation energy barrier of each elementary step involved in the reaction network on Pt(111). The calculated energetics were then incorporated into a comprehensive mean-field microkinetic model accounting for a total of 65 elementary steps. The model-predicted reaction rates were compared with the results from our reaction kinetics experiments on SiO2-supported Pt catalysts. Our results indicated that the hydrodechlorination of 1,2-dichloroethane on Pt(111) starts with a H-removal step; then, it proceeds through a sequence of alternating dechlorination and dehydrogenation steps until vinylidene (CH 2 C*) is formed; finally, CH 2 C* is hydrogenated to the final product, ethane, sequentially via vinyl (CH 2 CH*), ethylene, and ethyl (CH 3 CH 2 *) intermediates. After model parameter adjustments, we achieved good agreement between our theoretical model and experimental results; the adjustments to the calculated parameters are consistent with the typically anticipated coverage effects. Furthermore, our study offers valuable mechanistic insights, which are useful for improving catalysts for this chemistry.

1,2-dichloroethane↗
DOE OSTI2021

Mechanistic Similarities and Differences for Hydrogenation of Aromatic Heterocycles and Aliphatic Carbonyls on Sulfided Ru Nanoparticles

This study establishes the contrasting reactivity trends for the hydrogenation of aromatic hydrocarbons (AHCs = C n H m X, X = N, S, O, and C) and aliphatic carbonyls [R a C(O)R b ; R a = alkyl group, R b = CH 3 or H] on sulfided Ru clusters arising from the difference in the elementary proton and hydride attack catalytic sequence. Both reactions require sequential additions of a proton from either Ru n+ –(SH 2 ) or S 2 –(H δ+ ) species and a hydride from Ru n+ –(H δ– ) species to the unsaturated C=X bonds. For the five-membered-ring aromatic heterocycles (AHCs = pyrrole, thiophene, and furan), an initial proton addition limits the catalytic turnovers; thus, their hydrogenation reactivity increases with increasing gas-phase proton affinities of the AHCs. Pyridine as the more basic six-membered N-AHC is more susceptible to protonation; therefore, it is more reactive, and its initial proton addition is quasi-equilibrated, followed by the kinetically relevant hydride addition. Conversely, aliphatic carbonyls prefer to undergo hydrogen additions in a reverse sequence, where a Ru n+ –(H δ– ) hydride initially attacks the electron-deficient carbonyl C atom as the kinetically relevant step before a subsequent rapid S 2 –(H δ+ ) proton addition on the electron-rich O atom, as confirmed by isotopic exchange studies with butanal-D 2 and 1-butanol-D 2 mixtures and density functional theory calculations on S-deficient RuS 2 (100) surfaces. For these reasons, their hydrogenation reactivity increases with increasing gas-phase hydride affinities of the carbonyls. On metallic Ru surfaces without sulfur, hydrogen adatoms (H*) are the only reactive hydrogen species; the reactivity of their attack on aromatic heterocycles increases with increasing reactant proton affinities much more sensitively than that on sulfided Ru surfaces. This work illustrates the distinct catalytic roles of the diverse hydrogen species in hydrogenation—the interplay between proton and hydride additions has marked catalytic consequences in shaping the free energy landscape of the reactions, which in turn leads to the observed kinetic dependences, kinetic parameters, reactivity trends, and scaling relations between the measured barriers and the appropriate kinetic descriptors, that is, proton affinity of AHCs and hydride affinity of carbonyls in hydrogenation catalysis. Here, these mechanistic similarities and differences provide explanations of the observed reactivity trends and thus have profound implications for industrial hydrogenation and hydrotreating catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Kinetic and X-ray Absorption Spectroscopic Analysis of Catalytic Redox Cycles over Highly Uniform Polymetal Oxo Clusters

Metal–organic framework materials (MOFs) offer an opportunity for investigating catalytic properties of polymetal oxo clusters that are highly well defined and uniform in nature, in contrast to other classes of catalysts that may exhibit a propensity toward active site heterogeneity. We report herein a kinetic and X-ray absorption spectroscopy (XAS) analysis of the two-electron oxidation of CO over divalent metal sites in MIL-100(M = Fe, Cr) (MIL = Materials of Institut Lavoisier) materials carrying μ 3 -oxo bridged trimers, and connect observations about the kinetic relevance of redox steps to density functional theory (DFT) predictions published previously. The high degree of uniformity evident from in situ titration measurements leads to a congruence in mechanistic inferences made from steady-state catalytic, transient stoichiometric, isotopic exchange, and isotopic tracer data that all point to a sequential mechanism comprised of separate oxidation and reduction half-cycle steps conjoined by an active oxygen intermediate. In situ XAS data reinforce mechanistic conclusions derived from kinetic analysis, and suggest that the active oxygen intermediate may be more appropriately characterized as an iron-oxyl (Fe 3+ –O – ) rather than an iron-oxo (Fe 4+ =O 2– ) species. The Cr analogue of MIL-100 exhibits contrasting rate features that can be rationalized using an identical sequence of steps as MIL-100(Fe), but with a highly dissimilar set of kinetic parameters that can also be validated using transient stoichiometric experiments. The larger coverages of active oxygen intermediates on MIL-100(Cr) are consistent with predictions from prior DFT studies that suggest more stable and less reactive active oxygen species for metals with lower d-electron counts, and point to metal identity as a lever for precisely controlling the kinetic relevance of oxidation and reduction half-cycles in catalytic redox sequences over polymetal oxo clusters. Importantly, the results presented point to the utility of developing broadly applicable structure–catalytic property relationships over MOF nodes specifically, and highly uniform catalysts more generally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Microscopic Investigation of H 2 Reduced CuO x /Cu(111) and ZnO/CuO x /Cu(111) Inverse Catalysts: STM, AP-XPS, and DFT Studies

Understanding the reduction mechanism of ZnO/CuO x interfaces by hydrogen is of great importance for advancing the performance of industrial catalysts for CO 2 hydrogenation to methanol. Here, the reduction of pristine and ZnO-modified CuO x /Cu(111) by H 2 was investigated using ambient pressure scanning tunnelling microscopy (AP-STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT). The morphological changes and reaction rates seen for the reduction of CuO x /Cu(111) and ZnO/CuO x /Cu(111) are very different. On CuO x /Cu(111), perfect "44" and "29" structures displayed a very low reactivity towards H 2 at room temperature. A long induction period associated with an autocatalytic process was observed to enable the reduction by the removal of chemisorbed non-lattice oxygen initially and lattice oxygen sequentially at the CuO x -Cu interface, which led to formation of oxygen deficient "5-7" hex and honeycomb structures. In the final stages of the reduction process, regions of residual oxygen species and metallic Cu were seen. The addition of ZnO particles to CuO x /Cu(111) opened new reaction channels. On the ZnO sites, the dissociation of H 2 was fast and H adatoms easily migrated to adjacent regions of copper oxide. This hydrogen spillover substantially enhanced the rate of oxygen removal, resulting in the rapid reduction of the copper oxide located in the periphery of the zinc oxide islands with no signs for the reduction of ZnO. The deposited ZnO completely modified the dynamics for H 2 dissociation and hydrogen migration, providing an excellent source for CO 2 hydrogenation processes on the inverse oxide/metal system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Stabilization of the Active Ruthenium Oxycarbonate Phase for Low-Temperature CO 2 Methanation

Interstitial carbon-doped RuO 2 catalyst with the newly reported ruthenium oxycarbonate phase is a key component for low-temperature CO 2 methanation. However, a crucial factor is the stability of interstitial carbon atoms, which can cause catalyst deactivation when removed during the reaction. In this work, the stabilization mechanism of the ruthenium oxycarbonate active phase under reaction conditions is studied by combining advanced operando spectroscopic tools with catalytic studies. Three sequential processes: carbon diffusion, metal oxide reduction, and decomposition of the oxycarbonate phase and their influence by the reaction conditions, are discussed. We present how the reaction variables and catalyst composition can promote carbon diffusion, stabilizing the oxycarbonate catalytically active phase under steady-state reaction conditions and maintaining catalyst activity and stability over long operation times. In addition, insights into the reaction mechanism and a detailed analysis of the catalyst composition that identifies an adequate balance between the two phases, i.e., ruthenium oxycarbonate and ruthenium metal, are provided to ensure an optimum catalytic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Polystyrene Hydrogenolysis to High-Quality Lubricants Using Ni/SiO 2

Pyrolytic and light-activated oxidation processes are leading technologies for utilizing polystyrene (PS) wastes. These approaches exhibit poor selectivities, use complex reactors, and require solvents. Hydrogenolysis is effective for deconstructing polyolefins, but its application to PS feedstocks has been limited. Herein, we demonstrate Ni/SiO 2 catalysts to facilitate PS (M w ≈ 97 kDa) hydrogenolysis to produce lubricant base oils possessing group IV properties, achieving maximum yields of 70% within 6 h at 300 °C and 70 bar of H 2 . Gas, liquid, and oil product yields are stable across reaction conditions, whereas hydrogenation of the PS aromaticity and reduction of the molecular weight benefit from higher temperatures and H 2 pressures. Time-dependent experiments underscore the importance of elevated H 2 pressure, revealing that PS hydrogenolysis occurs sequentially, with aromatic ring hydrogenation preceding degradation of the C–C backbone. Kinetic measurements with 1,2-diphenylethane as a probe molecule demonstrate that ring hydrogenation pis 3 orders of magnitude faster than internal C–C bond cleavage over Ni/SiO 2 . Ni/SiO 2 proves to be effective in the hydrogenolysis of heavier PS polymers and rigid commercial PS products. Conversely, flexibility and foam PS feeds result in Ni/SiO 2 deactivation, attributed to performance additives. Unlike polyolefins, the process produces very little methane and other light hydrocarbons. Furthermore, these findings expand the applicability of hydrogenolysis to PS feedstocks, offering a versatile solution and broadening the range of high-value products from PS to include lubricant base oils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Low-Temperature Direct Oxidation of Propane to Propylene Oxide Using Supported Subnanometer Cu Clusters

Propylene oxide, a key commodity of the chemical industry for a wide range of consumer products, is synthesized through sequential propane dehydrogenation and epoxidation reactions. However, the lack of a direct catalytic route from propane to propylene oxide reduces efficiency and represents a major challenge for catalysis science. Herein, we report the discovery of a highly active and selective catalyst, made of alumina-supported subnanometer copper clusters, which can directly convert propane to propylene oxide at temperatures as low as 150 °C. Moreover, at higher temperatures, on the same catalysts, the selectivity is switched to propylene. Accompanying theoretical calculations indicate that partially oxidized and/or hydroxylated clusters have low activation energies for both propane dehydrogenation and propylene epoxidation pathways, enabling direct conversion with very high selectivity for propylene oxide. The discovery of a low-temperature catalyst that can convert propane directly to propylene oxide provides an important opportunity for the development of energy-efficient and economic catalysts for this industrially critical process. Similarly, when operating at higher temperatures, these catalysts are posed as potent oxidative dehydrogenation catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Spatially Patterned Architectures to Modulate CO 2 Reduction Cascade Catalysis Kinetics

Electrochemical CO 2 reduction using renewable sources of electrical energy holds promise for converting CO 2 into fuels and chemicals. The complex interactions among chemical/electrochemical reactions and mass transport make it difficult to analyze the effect of an individual process on electrode performance based only on experimental methods. Here, we developed a generalized steady-state simulation to describe an electrode surface in which sequential cascade catalysts are patterned in a periodic trench design. If appropriately constructed, this trench geometry is hypothesized to be able to yield a higher net current density for a CO 2 reduction (CO 2 R) cascade reaction. We have used realistic experimental reaction kinetics to investigate the role of trench geometry in mass transport, local microenvironments, and selectivity for a model CO 2 R cascade reaction. The model considers local concentration gradients of bicarbonate species at quasi-equilibrium and catalytic surface reactions based on concentration-dependent Butler–Volmer kinetics. Our results suggest that varying the spatial distribution of active sites plays a significant role in facilitating effective mass transport between active sites, modulating selectivity for the cascade reaction, and enhancing the yield of desirable cascade products. Moreover, we observe that this trench geometry significantly alters the cascade reaction rate by affecting the local pH, which can cause inadvertent depletion of available aqueous CO 2 to limit the CO 2 R cascade kinetics and modest suppression of the hydrogen evolution reaction (HER). The results highlight the trade-offs between mass transport, pH, and reaction kinetics that become apparent only when considering the coupled physics of all processes at the electrode surface. Here, this model can thus serve as a primary tool to build more selective and efficient patterned architectures for the CO 2 R cascade catalysis.

CO2 reduction↗
DOE OSTI2025

Reaction Pathways over ZnZrO 2 -Based Catalysts and Catalytic Sorbents

Reactive capture and conversion (RCC) is a process intensification approach that integrates CO 2 capture and hydrogenation within a single unit, removing the CO 2 purification and storage steps of traditional process flow schemes. This alters the catalytic step from a traditional steady-state (SS) flow process to a transient capture and conversion cycle, which could lead to product distributions distinct from those observed in conventional SS experiments. Such differences are investigated in the combined capture and hydrogenation of carbon dioxide to methanol over a ZnZrO 2 catalyst and a ZnZrO 2 + NaNO 3 /Mg 3 AlO x catalytic sorbent (CS) using fixed-bed kinetic measurements, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and steady-state isotopic transient kinetic analysis-DRIFTS (SSITKA-DRIFTS). Under SS conditions, ZnZrO 2 produced methanol through sequential hydrogenation of HCOO* and CH 3 O* intermediates. On the contrary, CO was attributed primarily to CO 2 dissociation at oxygen vacancies, as supported by isotopic shifts and measured reaction orders. For the CS, isotopic switching experiments suggested that monodentate carbonate species (CO 3 2− , abbreviated as m-CO 3 2− ) act as active intermediates that can be hydrogenated to HCOO* and subsequently to CH 3 O. Under RCC conditions, in situ DRIFTS and isotopic experiments reveal that m-CO 3 2− species formed during the CO 2 capture step follow two competing routes upon H 2 exposure: (i) direct hydrogenation to methane on the sorbent domain or (ii) migration of m-CO 3 2− to the ZnZrO 2 domain, where they are hydrogenated to methanol through the HCOO pathway. Overall, RCC enables carbonate hydrogenation routes not observed under SS cofeed conditions. Thus, the reaction pathways and rates during RCC can be different from operation under conventional SS conditions, and the product distribution is determined here by competition between carbonate hydrogenation on sorbent sites and migration to ZnZrO 2 for methanol synthesis.

CCUS↗
DOE OSTI2023

Molecular Nature of Mineral-Organic Associations within Redox-Active Mountainous Floodplain Sediments

Floodplains are critical terrestrial-aquatic interfaces that act as hotspots of organic carbon (OC) cycling, regulating ecosystem carbon storage as well as export to riverine systems. Within floodplain sediments, regular flooding and textural gradients interact to create dynamic redox conditions. While anaerobic protection of OC upon burial is a well-recognized carbon storage mechanism in redox-active floodplain sediments, the impact of protective mineral-organic associations is relatively unknown. Here we determined the quantitative importance and chemical composition of mineral-organic associations along well-defined redox gradients emerging from textural variations and depth within meander sediments of the subalpine East River watershed (Gothic, CO). Here we characterized mineral-organic associations using a combination of sequential extractions, physical fractionation, and high-resolution mass spectrometry. Across the meander, we found that mineral-associated OC constitutes a significant fraction of total OC, and that extractable iron (Fe) and aluminum (Al) phases as well as high-density isolates were strongly correlated with total OC content, suggesting that mineral-organic associations are quantitatively important for floodplain sediment OC protection. Our mass spectrometry results showed OC associated with increasingly ordered Fe and Al phases are relatively enriched in low-molecular weight, oxidized, aromatic compounds. Surprisingly, however, total OC content showed weak or no correlation with indicators of anaerobic protection, such as relatively bioavailable OC pools (water-extractable and particulate OC) or the molecular weight and oxidation state of OC. Overall, this work highlights that protection of OC bound to reactive mineral phases-in addition to anaerobic protection-can play a quantitatively important role in controlling soil carbon storage in redox-active floodplain sediments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Inelastic Neutron Scattering Observation of Plasma-Promoted Nitrogen Reduction Intermediates on Ni/γ-Al 2 O 3

Plasma-assisted catalysis is an emerging technology for the atmospheric pressure and low bulk gas temperature synthesis of ammonia from molecular nitrogen and hydrogen. Direct evidence for plasma-induced surface reaction intermediates relevant to ammonia production, including surface hydrides and NH x (x = 1, 2, 3) species, has remained elusive. In this work, we report inelastic neutron scattering (INS) observations of alumina-supported Ni particles after treatment with N 2 and H 2 plasmas. INS experiments reveal the presence of NH x species and hydrides on Ni sites after exposure to sequential N 2 and H 2 plasma treatments. By separating exposure, we exclude the presence of plasma-phase reactions and demonstrate that these species are generated through plasma-facilitated surface reactions. Computed synthetic INS spectra of NH 3 , NH 2 and NH adsorbates on Ni support the experimental assignments of surface intermediates. The results directly implicate plasma stimulation of dinitrogen in generation of surface-bound nitrogen that participates in further hydrogenation reactions driven either thermally or with H 2 plasma.

36 MATERIALS SCIENCE↗
DOE OSTI2022

What Would It Take to Manufacture Perovskite Solar Cells in Space?

Imagine: Astronauts land on the moon. They verify their arrival with mission control and perform system checks and validations. After the dust settles, they open the airlock of the landing vehicle and venture outside. A side hatch opens, and a flexible substrate slowly unfurls on a boom. A series of printer heads raster, hovering over the substrate and sequentially vapor-depositing the constituent layers of a perovskite solar module. In time, a 1-megawatt array has been manufactured on the moon and can now be connected to supply power to the Artemis Base Camp. This ambitious vision could someday become a reality.

14 SOLAR ENERGY↗